Coloration of materials comprising cellulose derivatives



phenol, monacetyl-m-aininophenol, dimethyl-m- Patented Nov. 21, 1933 v 1 UNITED {STATES PATENT or c;

ooLonA'rIoN or MATERIALS COMPRISING CELLULOSEIDERIIVATIVES George Holland Ellis, Denis Hou'ghton Mosby,'

and Henry Charles Glpin, Spondon, near Derby,

England, assignors to Celanese Corporation of 2 America, a corporation of Delaware No Drawing. Application August 2, 1928, Serial No. 297,098, and in Great B rit ain January 30,

192s I I organic esters of cellulose, for example cellulose formate, propionate or butyrate or the products;

obtained by treatment of alkalized cellulose with esterifying agents (e. g. the product known as immunized cotton made with p-toluene sulphcchloride), or made with or containing cellulose ethers, for instance methyl, ethyl or benzyl cellulose or the corresponding condensationprod- 'ucts of cellulose and glycols or other polyhydric alcohols, .all of which cellulosederivatives are. hereinafter referred to as organic substitution derivatives of cellulose.

We have found that colorations which are particularly valuable can be obtained on materials made with or containing cellulose acetate or other 2 organic substitution. derivatives of cellulose by means of azo dyes and preferably unsulphonated dyestuiis containing the anthraquinone nucleus and accordingly the. present invention comprises I applying the said. azo dyes in substance to the materals or forming themon the materials.

The azo dyes may be prepared either in substance or upon the material by diazotizing primary 'anthraquinones or derivatives thereof and coupling or developing with any suitable components, for example p-xylidine,' cresidines,

anisidines, m-toluidine, m-phenylenediamine, nitro-m phenylenediamine, "phenol, maminoaminophenol, u-naphthylamine, w-hydroxyethylm-naphthylamine, 1 -chlor-}8-hydroxypropyl-a- I naphthylamine, {i-naphthylamine, 1-ami'no-2 methoxy-naphthalene, aminonaphthoic acids and side-chain and nuclear substitutions thereof, etc. For producing the dyestuffs on the fibre or matev.rial, the amino-anthraquinone or derivative thereof may, for example, be applied first diazotized on the material and developed,- or the coupling component. may beapplied first and developed with a .diazotized derivative of'anthra quinone. a I

'The anthraquinone nuclei, in addition to con taining a group or groups necessary for the formation of the azo dyes, may contain any other desired substituent groups, for example, carboxyl, 'alkyl, halogen, amino, alkyl-amino, acidylarnino, nitro, hydrcxy, alkoxy and mercapto groups.

The following are examples of azo dyes which may be applied according to the present invention, but it will be understood that the listing 2 Claims. I

.of these examples implies no invention thereto. 7 I

limitation of the co le 1 Component p i g e g up Shade I l-aminoanthraquinone Phenol Yellow l-aminoanthraquinone m-toluidine Yellow I l-aminoanthraquinone o-anisidine I Golden oronge l-aminoanthraquinone m-phenylene diamme yellowish-brown l-aminoanthraquinone Anthranilic acid Golden orange ,65

l-aminoanthraquinone fi-amgionaphtholc Bluish-red o aci 1 1,- amino; 2 methyl Phenol Yellow I anthraquinone' i l amino 2 methyl m-toluidine Golden orange anthraquinone I 1 amino 2 methyl Dimethyl -m'- ammo Orange anthraquinone I c I I I 70.

1 amino 2 methyl m-phenylenc dlamme Golden brown anthraquinone 1-aminoanthraquinonem-toluidine Golden yellow Z-carboxylic acid 1 I 1 1' amino 4 hydroxy Phenol Browmsh-yellow anthraquinone 1 amino 4 hydroxy m-toluidine Golden yellow I ,75

anthraquinone r 1 amino 4 -;hydroxy m-phenylenc diamine Greenish-black anthroquinone 1 amino 4- acetyl B-aminonaphthorc Red-brown I amino-anthraquinone ac I 1 II 1:4 diamino anthrafi-aminonaphthow Red-brown I quinone diazotized acid (1 mol. I I

1:5 diamino anthra- Phenol (1 mol.) Golden brown 30 quinone (diazotized) I II n 1:5 diamino anthra-- m-toluidme (1 mol.) Orange quinone (diazotized) I I II 1:5 dia mino anthra- Phenol (1 mol.) and Orange III quinone(tetrazotized) ni-toluidme (111101.) 1 a 1:8 diamino anthra- Phenol (1 mol.) II Golden orange:

quinone (diazotiz'ed) I II 1:8 diamino anthram-toluidine (1 mol.) 1 Orange J qui none (diazotized) :1

1:8 diamino anthra' m-phenylenediamme Browmsh-red quinone (diazotized) (1 mol. I

Z-aminoanthraquinone fl-omiinonaphthoic 1 Orange-red I am I I The dyestuffs t o be applied in substance or the components (for 'forming the dyes on the fibre) where insufiiciently soluble in wa ter, may be applied to the goods in aqueous suspension or dis-a persion, obtained, for example, by colloidal grind- II ing, by dissolving in a solvent and mixing with water containing or not containing a protective co1loid,'by pretreating with dispersing ag ents or by other methods. "As dispersing agents suitable for obtaining such dispersions those described in prior U. S. PatentsNos. 1 ,618,413, 1,618,414, and 1,694,413, and 1,840,572 dated'Jan. 12,"1932'and 1 ,716,721 dated June 11, 1929 may be instanoed, viz bodies of oily or'fatty characteristics, namely higher fatty acids or sulphonate or'otherderiva mg,

tives thereof containing saltforming groups, such as sulphoricinoleic-acid or other sulphated'fatty' acids or saltsof such acids or bodies, for instance their alkali or am'monium salts, used alone orinc conjunction with auxiliary solvents as'described'i m The following examples illustrate the dyeing of goods according to the present invention, but are not to'be regarded as in any way limiting its scope.

Example 1 To dye a yellow shade on 10 kilogramsof cellulose acetate knit fabric, 400 grams of anthraquinone-l-azo-m-toluidine 25% aqueous paste are finely ground and there are added with stirring 300-400 grams of the sulpho-aromatic fatty acid product prepared as follows:-

25 kilograms of naphthalene are mixed with 25 kilograms of oleic acid by warming to C. The mass is then cooled quickly and the resultant paste is added slowly to 100 kilograms of 20% oleum with vigorous agitation, the temperature being kept below 40 C. When the addition is complete the temperature is raised very gradually to 100 C., at which it is maintained for 3 hours. Care is needed during this heating to prevent a frothing. After cooling, the mixture is poured into 250 litres of water and treated with 50 kilograms of common salt. The whole is allowed to separate, when the top aqueous layer is decanted off leaving an oily product which is washed several times with 20% brine.

The mixture is heated until the maximum degree of'dispersion is achieved and then diluted with boiling water and added through a sieve into a suitable dyeing machine containing 300 litres of water. The goods are entered, and processed with rising temperatures according to the common methods of dyeing until the shade is achieved. The, goods are now lifted, rinsed and dried, or otherwise treated as requisite.

Example 2 To dye an orange shade on 10 kilos of cellulose acetate yarn in hank form, 100 grams of finely ground Z-methyl-anthraquinone-l-azo-dimethylmetaamino-phenol are well stirred or ground with 1 litre of sodium sulphoricinoleate (50%); the mixture is heated under an open steam pipe and then diluted with boiling water and further boiled. The liquor is then passed through a filter-cloth into a dyebath containing 300 litres of cold soft water. 10kilos of the material are introduced and dyeing carried out as usual, the temperature being raised'to 75-80 C., and maintained at this figure as necessary to exhaust. The hanks are now lifted, rinsed, and dried or otherwise treated as requisite.

Example 3 To dye lOkilos of cellulose acetate knitted goods a golden orange shade, 100 grams of anthraquinone-l-azo-anthranilic acid are dissolved as the ammonium salt in a dyebath containing 300 litres of water, and the previously wetted out goods entered. The temperature is raised slowly to 75-80 C., and maintained at this figure till the requisite depth is achieved. Exhaustion may be assisted by addition of 2-3% formic acid on weight of goods towards the end of the dyeing operatlon. The goods are now lifted, rinsed, and dried or otherwise treated as requisite.

esaeza Example 4 To dye 10 kilos of cellulose acetate knitted goods a bluish red shade, 200 gramsofanthraquinone-1-azo-2-amino-3-naphthoic acid are dissolved as the ammonium salt in a dyebath containing 300 litres of soft water, to which 1 cc. per litre of Turkey Red Oil (50%) has been added. The previously wetted out goods are now entered,and the temperature raised slowly to 75-80" C., and maintained at this figure'till the requisite.

Example 5 To dye a red-brown shade on 10 kilos of cellulose acetate yarn in hank form, 200 grams of the dyestuffs i-amino-anthraquinone-l-aZo-2- amino-B-naphthoic acid are well stirred with 1 litre of sodium sulphoricinoleate (50%). The mixture is heated under an open steam pipe till a good dispersion is obtained and then diluted with boiling soft water. The liquor is then passed through a filter cloth into a dyebath containing 300 litres of cold soft water. The material is then entered, and dyeing carried out as usual, the temperature being raised to 75-80 C., and maintained at this figure as necessary to exhaust. The hanks are now lifted, rinsed, and dried or otherwise treated as requisite.

In a similar manner other azo dyestuffs containingv anthraquinone nuclei may be used to color cellulose acetate, and furthermore, colorations may be similarly obtained on materials comprising other organic substitution derivatives of cellulose, for example cellulose formate, cellulose butyrate, immunized cotton, methyl or ethyl cellulose etc.

Azo dyestuffs containing diazctizable amino requisite shade is obtained. The goods are now lifted, rinsed, and dried or otherwise treated as lie groups may be diazotized on the material to produce further dyestuifs.

Mixed goods containing for example, in addiaccording to the present invention with or with.

out employment of other dyestuffs or components according to the character of the threads or fibresused in association.

The term coloring used in the claims is to be understood to include all methods of coloring and more particularly dyeing, printing and stencilling.

What we claim and desire vto secure by Letters Patent is:--

1. Process for coloring materials comprisingorganic substitution derivatives of cellulose, com- 

